Miticidal dihydrazide composition



Patented Dec. 22, 1953 u-Nrreo 236631561iifidrjbai,nlfiiiiinAzliiijidoMfdslfio ii taeosssuctmuflaikg N. Y.,assignor to Mana Qhemical Corporation, g-inia aicq noraticnz 1-.Vinlglobrayving Applicaticin ifiilyj Ila-1956i ScriaL-No. 153;250

airnv ntion e ate ft mp bv ntp si fif fi. cpntroljof mitesjandj'redspiders; and, to imp'mva m s h e ral, ff

t ,sec ic l'. m o lq a, pr e insecticidal, compositions. tojwhibeenimpartedspecific;miticidalf act'iv i t it I, u h'vtet xict tfiiec s.n jan, m r ved et controlling and eliminating f' spiders, European redmites' byway of, le

ieusne s i'at eckjcnn ants' mess s Q f s r y i ther nsec sj-whichfno i 2mally, feed on; the: redgspidersendf keep fthem underli pt e e deri g" hm ac'tive'bu must lso" e quttip yww c tioni ni hei t is -particularlyimortant sin ha e bee st d. nd.

iet a 'sl rein fnd 9. .10 v 'esin eth yiiig; he" est l slwifn es ry. he?host.

Accordingeltoitlie present invention, specific miticidal activitywithout phytotoxic efiect is parted tq n ct eid llcomp on ei-disersing'a small proportion of a moderately watersoluble 'acyclicfdihyglrazide of an aliphatic (1i.- carboxylic acid such'as adipic acidfiFan secticidal -carrier mediumj such as a" powder or aqueous spraysolution-J Witli particular adva'r'r tage, the powder or solutioncontains a compatible conventional insecticide of more general action sothat combined insecticidal activity of greater extent is obtained. Interms of the method aspect of my invention, a dilute dispersion ineither the form of powdered or liquid admixture or in solution of asmall proportion of the acyclic dihydrazide is formed, and thedispersion is applied to plants. I have found that the moderatelyWater-soluble aliphatic dihydrazides, for example adipic dihydrazide,have surprising activity in dispersed form in protecting plants againstmites and red spiders even though they appear to be ineffective againstother common organisms such as aphids, milkweed bugs,

} rial-T "representative 0 7 acid-) have goo-d1 activ y increasingphytoto'xicity tainin pyropliyllit ta Mexican? bean; beetles a'ndrb11135] southrm army; wicrmaa-ndsarciwithoutapparehtnhytotoxiciactiomatrefiectiver dilutions? ,Thfii non-fungicidal: and:nomphytotoiiic:ptopertie'sio the-:h'ydrazides .arei

. surprising since armellr-known phytntoxicf: sub-e stance is. the'soecalledrmaleicc hydrazidea which n howeven has; theicyclicsimide"structure-:1

Hence, the compositionsmfimyrinventiozr coni tain as an essentialvactiyejngredient an acyclic aliphatic dicarboxylic acids, such asDimelicnsubericand sebacic (sebacic cr carbon ato'ms acid'i'. Sllbditiyhydraz-ides; I (Ina-ionic 'a'cid is The us'eful hydrazid'es iinpartspecific activity whenidispei sed=or dissolvetl I aqueeu' 'solfitionsixam-pies ofusefu p6 'oth wettabl poiifdeif's an kislgii ilirf gypsumg'ch" powdereii' materia V d fur. Because of the apparent significance ofwater solubility in effecting control of mites, it is advantageous toadd a hygroscopic agent, e. g. glycerine or ethylene glycol, to the dustcompositions. When dispersed in aqueous solution, suspending, wetting oremulsifying agents, such as an alkylated aryl polyether alcohol or analkyl aryl sulfonate are advantageously employed. As the molecularWeight of the hydrazide increases up to sebacic acid dihydrazide, forexample, the miticide imparting agents tend to become water insoluble sothat they should be mechanically or chemically dispersed in aqueousmedia. The dispersions may comprise aqueous emulsions in which thehydrazide, advantageously together with a compatible insecticide ofcomplementary activity, is dissolved in an organic solvent such asrefined kerosene, alcohol, acetone, benzene or xylene and dispersed inaqueous emulsion with the aid of an emulsifying agent.

The proportions of miticide-imparting agent employed according to myinvention are small, of the order of about 0.5 to 5 weight per cent. Forexample, aqueous dispersions of 2 per cent concentration have been foundto be particularly efiective spray solutions.

The hydrazide dispersions and solutions may be applied in theconventional way as by spraying. As noted above, the solutionsadvantageously will contain one or more additional insecticides and/orfungicides. For example, an aqueous spray emulsion may contain DDT anddispersed finely divided sulfur, the sulfur acting to control applescab, the hydrazide to kill red spiders'and the DDT to kill other commonorganisms. In similar manner the hydrazide may be dispersed in apowdered composition and applied to plants so as to control a variety ofpests.

The usefulness of the new compositions of my invention and of thegeneral method of application will be illustrated in the followingexamples. In the examples adipic dihydrazide is employed asrepresentative of otherhydrazides and the particularcompositionsdescribed are spray solutions. The preparation ofdispersions in other forms and containing other materials will beobvious from the above description.

E sample I Cranberry bean plants were infected with greenhouse redspiders and sprayed with various concentrations of adipic dihydrazide inaqueous solution containing one part in five thousand of Triton X-155 apolyoxyethylene phenol ether as wetting agent. The plants were sprayeduntil the solution dripped 01f the leaves. Using a, 2 per centconcentration of adipic dihydrazide and repeating the treatment afterthree days in one case and after five days in a second. case, the plantswere found to be substantially free of red spiders when observed after2, 9 and 12 days. Very fewspiders were able to migrate to new leavesindicating that a high degree of control was obtained. Using the sameconcentration of dihydrazide, control with very little migration wasnoted after 12 days even when the plant was sprayed only once. Almostasgood results were obtained using a spray having a concentration of l percent of adipic dihydrazide and fair results were obtained using 0.5 percent of active ingredient. In a check run, the dihydrazide was omittedand the Triton solution applied. Under these conditions the red spiderswere not affected and migrated'freely to new leaves.

4 Example II The procedure of Example 1'. was repeated with theexception that the plants were sprayed first and subsequently infectedwith red spiders. Under these conditions the red spiders were onlyslightly less effectively controlled, fair results being obtained in'twoto five days but with very satisfactory results after 10 days. The 0.5per cent concentration of dihydrazide gave comparatively poor resultswith moderate migration of the spiders. Again the check on the Tritonsolution alone gave no control whatever.

Example III Cranberry bean plants infected with greenhouse red spiderswere dipped in a 2 per cent solution of adipic dihydrazide containing0.5 per cent of Nacconol an alkyl aryl sulfonate as a wetting agent. Onegroup of plants was dipped once and showed fair to good control withsubstantially no migration. When the plants were dipped twice at either3- or 5-day intervals,- excellent control was obtained nd no migrationoccurred. Under the same conditions a check without the dihydrazide inthe Nacconol solution showed no action whatever and the organismsmigrated freely.

I claim:

l. A composition having miticidal activity which consists essentially ofa dispersion of about. 0.5 to 5 weight per cent of an acyclicdihydrazide-I of an aliphatic dicarboxylic acid in an inert com--patible powder as carrier said acid being saturated, unsubstituted andstraight chain, and; containing from 3 to 10 carbon atoms.

2. A composition having miticidal activity which consists essentiall ofa dispersion of about; 0.5 to 5 weight per cent of adipic dihydrazide iman inert compatible powder as a carrier.

3. The method of controlling mites and red spiders which comprisesdispersing an acyclic: dihydrazide of an aliphatic dicarboxylic acid in;an insecticidal carrier medium and applying the; dispersion to plants,said acid being saturatedi. unsubstituted and straight chain, andcontaining: from 3 to 10 carbon atoms.

4. The method of controlling mites and red spiders which comprisesdispersing adipic dihydrazide in an insecticidal carrier medium andapplying the dispersion to plants.

JACOB snoan. I

References Cited in the file of this patent Curtius: Journal fiirpraktische Chemie, Band 199, Nelle Folge 91, pages 3 t0 5 (1915).

ume 33, pages 669 to 6'76, August 1940..

1. A COMPOSITION HAVING MITICIDAL ACTIVITY WHICH CONSISTS ESSENTIALLY OFA DISPERSION OF ABOUT 0.5 TO 5 WEIGHT PER CENT OF AN ACYCLIC DIHYDRAZIDEOF AN ALIPHATIC DICARBOXYLIC ACID IN AN INERT COMPATIBLE POWDER AS ACARRIER, SAID ACID BEING SATURATED, UNSATURATED AND STRAIGHT CHAIN, ANDCONTAINING FROM 3 TO 10 CARBON ATOMS.